Kinetic and Molecular Weight Modeling of Miniemulsion Polymerization Initiated by Oil‐Soluble Initiators

Abstract

A mathematical model for the miniemulsion polymerization initiated by oil‐soluble initiators is described in detail with comparisons to experiment results. The desorption of primary radicals and particle population balance are introduced to illustrate the distribution of radical per particles. The effects of different variable factors including the particle size, surfactant layer, initiator, and aqueous phase inhibitor are considered, and the model predictions coincide well with experiment results under different above‐mentioned conditions. The model is found to be useful in explaining the ongoing debate about the origin of effective radical in miniemulsion polymerization initiated by oil‐soluble initiators. It is found that the effective radicals are originated from the primary radicals desorbed from the particles, and the contribution of the small amount of initiator dissolved in the aqueous phase can be ignored. image